CN117642477A - Solvent-free adhesive composition and laminate made therewith - Google Patents

Solvent-free adhesive composition and laminate made therewith Download PDF

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Publication number
CN117642477A
CN117642477A CN202180100199.3A CN202180100199A CN117642477A CN 117642477 A CN117642477 A CN 117642477A CN 202180100199 A CN202180100199 A CN 202180100199A CN 117642477 A CN117642477 A CN 117642477A
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China
Prior art keywords
polyol
group
adhesive composition
solvent
weight
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CN202180100199.3A
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Chinese (zh)
Inventor
白晨艳
T·施密特
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/3885—Phosphate compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is a solvent-free adhesive composition comprising: (A) An isocyanate component obtained by the reaction of reactants comprising: at least one monomeric cycloaliphatic isocyanate compound comprising at least one cyclohexyl (cyclohexylidene) group and at least one first polyol; and (B) a polyol component comprising a specifically selected functionalized and nonfunctionalized polyol. The solvent-free adhesive composition can be used to produce laminates, such as laminated packaging materials, which well meet the requirements of various food compliance regulations and have excellent performance characteristics (such as heat resistance and chemical resistance). A method for producing the laminate and the resulting laminate are also disclosed.

Description

Solvent-free adhesive composition and laminate made therewith
Technical Field
The present disclosure relates to a unique solvent-free (SL) adhesive composition, a laminate produced using the adhesive composition, and a method for producing the laminate. Laminates comprising an adhesive layer derived from a solvent-free adhesive composition meet the requirements of various food compliance regulations well and exhibit excellent performance characteristics such as good heat resistance and chemical resistance, as evidenced by good bond strength after heat treatment.
Background
The adhesive composition can be used in a wide variety of applications. For example, they may be used to bond substrates such as polyethylene, polypropylene, polyester, polyamide, metal, paper or cellophane to form composite films, i.e. laminates. The use of adhesives in different lamination end use applications is generally known. For example, adhesives may be used to make films/films and film/foil laminates that are commercially used in the packaging industry. Laminates comprising metal foils are widely used for their desirable properties, such as good light barrier properties, gas/moisture barrier properties. However, foil-containing laminates prepared by using SL adhesives face two challenges: the first challenge is that it is difficult to achieve good appearance when the production line is running at high speed, and the second challenge is that it is difficult to maintain good mechanical properties (such as bond strength) after heat treatment (such as hot filling or cooking). Accordingly, there has long been a need to develop a unique adhesive that can be used to produce laminated packaging materials exhibiting desirable optical properties, heat resistance, and good mechanical strength at high production rates.
After continued exploration, we have surprisingly developed a unique SL adhesive composition that can achieve the above objectives.
Disclosure of Invention
The present disclosure provides a unique SL adhesive composition, a laminate (e.g., a laminated packaging material) prepared by using the SL adhesive composition, and a method for preparing the laminate.
In a first aspect of the present disclosure, the present disclosure provides a solvent-free adhesive composition comprising:
(A) An isocyanate component comprising a prepolymer, the prepolymer being the reaction product of reactants comprising: (a) At least one monomeric cycloaliphatic isocyanate compound comprising at least one cyclohexyl (cyclohexylene) group and at least two isocyanate groups; and (b) at least one first polyol selected from the group consisting of: a first polyester polyol, optionally a first polyether polyol, optionally a first polycarbonate polyol, and combinations thereof, wherein the prepolymer comprises more than one free isocyanate group; and
(B) A polyol component comprising at least one second polyol selected from the group consisting of: carboxylic acid functionalized polyols having hydroxyl groups and acid side groups, phosphorus functionalized polyols comprising at least one phosphate group, second polyester polyols, second polyether polyols, and any combination thereof.
In a second aspect of the present disclosure, the present disclosure provides a laminate (e.g., a laminate packaging material (particularly a packaging material for packaging food products) comprising at least one first substrate, at least one second substrate, and at least one adhesive layer sandwiched therebetween, wherein the adhesive layer is derived from a solvent-free adhesive composition according to the present disclosure, and each of the first substrate and the second substrate is independently selected from the group consisting of a metal foil, a polymer layer, a fabric layer, and combinations thereof.
In a third aspect of the present disclosure, the present disclosure provides a method of producing a laminate of the present disclosure, the method comprising:
(a) Providing at least one first substrate and at least one second substrate; and
(b) The first substrate and the second substrate are bonded together by using the solvent-free adhesive composition of the present disclosure.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Furthermore, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.
As disclosed herein, "and/or" means "and, or alternatively. All ranges are inclusive of the endpoints unless otherwise indicated.
According to embodiments of the present disclosure, the adhesive composition is a "two-part" or "two-pack" composition comprising an isocyanate component (a) and a polyol component (B). According to another embodiment, the isocyanate component (a) and the polyol component (B) are packaged, transported and stored separately, and compounded shortly before or immediately before use in the manufacture of the laminate.
Without being bound by any particular theory, the technical breakthroughs of the present disclosure are primarily directed to specifically designed formulations of adhesive compositions. In particular, it was found that polyurethane systems prepared by using the following can be used as adhesives for laminates, such as foil-adhesive-polymer laminate packaging materials, exhibiting desirable performance characteristics: (A) Prepolymers derived from monomeric isocyanate compounds containing cyclohexyl (cyclohexylene) groups (e.g., cyclohexyl groups or cyclohexylene groups), polyester polyols, and optionally polyether/polycarbonate polyols, (B) polyol components consisting of carboxylic acid-functionalized polyols, phosphorus-functionalized polyols, polyester polyols, and polyether polyols. It has also been found that the type and relative content for each of the above components can be further varied to achieve further improvements in the performance characteristics of SL adhesives and laminates.
Isocyanate component (A)
According to embodiments of the present disclosure, the isocyanate component (a) has an average NCO functionality of at least about 1.5, or about 1.6 to 10, or about 1.7 to about 8, or about 1.8 to about 6, or about 1.9 to about 5, or about 2 to about 4, or about 2 to about 3, or about 2 to 2.5, or within a range of values obtained by combining any two of the endpoints above. For example, isocyanate component (a) has an average NCO functionality of 2.0.
According to an embodiment, the prepolymer contained in isocyanate component (a) is the reaction product formed by the reaction of: (a) At least one monomeric cycloaliphatic isocyanate compound comprising at least one cyclohexyl (cyclohexylene) group and at least two isocyanate groups; and (b) at least one first polyol selected from the group consisting of: a first polyester polyol, optionally a first polyether polyol, optionally a first polycarbonate polyol, and combinations thereof, wherein the prepolymer comprises more than one free isocyanate group, such as at least two free isocyanate groups. For example, the prepolymer has an average NCO functionality of greater than 1.0, or at least 1.5, or at least about 2.0, or about 2.0 to 10, or about 2.0 to about 8, or about 2.0 to about 6, or about 2.0 to about 5, or about 2 to about 4, or about 2 to about 3, or about 2 to 2.5, or an NCO functionality of 2.0, or within a range of values obtained by combining any two of the endpoints above.
According to embodiments of the present disclosure, monomeric cycloaliphatic isocyanate compounds used to prepare the prepolymer include isophorone diisocyanate (IPDI), various isomers of methylene-bis (cyclohexyl isocyanate) (HMDI), and mixtures of IPDI and HMDI. According to embodiments of the present disclosure, isophorone diisocyanate includes isophorone-1, 4-diisocyanate, isophorone-1, 2-diisocyanate, and isophorone-1, 3-diisocyanate. According to embodiments of the present disclosure, methylene-bis (cyclohexyl isocyanate) includes methylene-bis (4-cyclohexyl isocyanate), methylene-bis (3-cyclohexyl isocyanate), and methylene-bis (2-cyclohexyl isocyanate). According to a preferred embodiment of the present disclosure, isophorone diisocyanate has a molecular structure represented by formula IIIa, and methylene-bis (cyclohexyl isocyanate) has a molecular structure represented by formula IIIb.
According to an embodiment of the present disclosure, the content of (a) monomeric cycloaliphatic isocyanate compound is from 30% to 70% by weight, based on the total weight of isocyanate component (a), such as in the range of values obtained by combining any two of the following endpoints: based on the total weight of isocyanate component (a), 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, and 70 wt%.
According to an embodiment of the present disclosure, component (a) comprises only IPDI and/or HMDI as isocyanate raw materials for preparing the prepolymer, but does not comprise any isocyanate-functional compounds other than IPDI and HMDI. According to another embodiment of the present disclosure, the solvent-free adhesive composition does not comprise any isocyanate-functional compounds or precursors thereof other than IPDI and HMDI.
The present disclosure also includes embodiments in which isocyanate compounds other than the monomeric cycloaliphatic isocyanate compounds described above (particularly isocyanate compounds other than IPDI and HMDI) may be used, and such isocyanate compounds will be referred to in the context of the present disclosure as "secondary isocyanate compounds", "supplemental isocyanate compounds" or "additional isocyanate compounds". In embodiments comprising the secondary isocyanate compound, the secondary isocyanate compound may be part of the raw material used to prepare the prepolymer, i.e. may be combined with IPDI and/or HMDI for preparing the prepolymer of component (a). Alternatively, the secondary isocyanate compound may be a component independent of the prepolymer. Embodiments that include a combination of the two cases described above are also the concepts of the present disclosure.
According to embodiments comprising the secondary isocyanate compound, the secondary isocyanate compound may comprise one or more isocyanate compounds comprising at least two isocyanate groups, preferably comprising two isocyanate groups. According to an embodiment, the secondary isocyanate compound is selected from the group consisting of: c comprising at least two isocyanate groups 2 -C 12 Aliphatic isocyanates,C comprising at least two isocyanate groups 6 -C 15 Cycloaliphatic (in addition to the monomeric cycloaliphatic isocyanate compounds described above, in particular in addition to IPDI and HMDI) and combinations thereof. Exemplary secondary isocyanate compounds may be selected from the group consisting of: isomers of hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, hexamethylene diisocyanate ("HDI"), or mixtures thereof. According to an embodiment of the present disclosure, the isocyanate component (a) does not contain an aromatic isocyanate or an araliphatic isocyanate as a secondary isocyanate compound. According to another embodiment of the present disclosure, the content of the secondary isocyanate compound may be 1 to 50 wt%, or 2 to 45 wt%, or 5 to 40 wt%, or 8 to 35 wt%, or 10 to 30 wt%, or 12 to 25 wt%, or 15 to 20 wt%, or 15 wt%, or 12 wt%, or 10 wt%, or 8 wt%, or 6 wt%, or 5 wt%, or 2 wt%, or 1 wt% or 0 wt% based on the total weight of all isocyanate compounds (i.e., the combined weight of the monomeric cycloaliphatic isocyanate compound and the secondary isocyanate compound). Compounds having isocyanate groups, such as the prepolymers, IPDI/HMDI and secondary isocyanate compounds described above, can be characterized by the parameter "% NCO", which is the amount of isocyanate groups by weight based on the weight of the compound. The parameter% NCO can be measured by the method of ASTM D2572-97 (2010). According to embodiments of the present disclosure, the prepolymer and the secondary isocyanate compound may have a% NCO of at least 3 wt%, or at least 5 wt%, or at least 7 wt%. In some embodiments, the prepolymer and the secondary isocyanate compound have a% NCO of no more than 40 wt%, 35 wt%, 30 wt%, or 25 wt%, or 22 wt%, or 20 wt%.
According to an embodiment of the present disclosure, the starting materials for preparing the prepolymer of component (a) do not comprise Hexamethylene Diisocyanate (HDI) or any isomer/dimer/trimer/oligomer thereof. According to another embodiment of the present disclosure, the starting materials for preparing the prepolymer of component (a) do not comprise Xylylene Diisocyanate (XDI) or any isomer/dimer/trimer/oligomer thereof.
According to embodiments of the present disclosure, the first polyol used to prepare the prepolymer of component (a) may be selected from the group consisting of: a first polyester polyol, optionally a first polyether polyol, optionally a first polycarbonate polyol, and combinations thereof.
According to an embodiment of the present disclosure, the first polyester polyol has a hydroxyl functionality of at least 1.8, at least 2.0 and at most 2.2, or at most 2.5, or at most 2.8, or at most 3.0, or within a range of values obtained by combining any two of the above endpoints. The first polyester polyol may have a molecular weight of 500g/mol to 5,000g/mol, or 600g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a numerical range obtained by combining any two of the above endpoints. The polyester polyol is generally obtained by reacting a polyfunctional alcohol having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, with a polyfunctional carboxylic acid having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms or an anhydride/ester thereof. Typical polyfunctional alcohols used to prepare the polyester polyols are preferably diols, triols, tetrols, and may include ethylene glycol, butanediol, diethylene glycol, triethylene glycol, polyalkylene glycols, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylol benzene, and any combination thereof. Typical multifunctional carboxylic acids used to prepare the first polyester polyol may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and may be substituted, for example, with halogen atoms, and/or may be saturated or unsaturated. Preferably, the multifunctional carboxylic acid is selected from the group consisting of: adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, 2-methylsuccinic acid, 3-diethylglutaric acid, 2-dimethylsuccinic acid, trimellitic acid, anhydrides thereof, and any combination thereof. Adipic acid or a mixture of adipic acid and isophthalic acid is preferred. In another embodiment, the first polyester polyol has an OH number of 30mg KOH/g to 200mg KOH/g, preferably 40mg KOH/g to 180mg KOH/g, more preferably 50mg KOH/g to 160mg KOH/g. According to embodiments of the present disclosure, the content of the first polyester polyol may be 50 to 100 wt%, based on the total weight of the first polyol (b), such as within a range of values obtained by combining any two of the following endpoints: based on the total weight of the first polyol (b), 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 85 wt%, 88 wt%, 90 wt%, 92 wt%, 95 wt%, 98 wt% and 100 wt%.
According to embodiments of the present disclosure, the first polyether polyol has a hydroxyl functionality of from 1.8 to 3.0, such as at least 1.8, or at least 2.0, or at least 2.2, or at least 2.5, or at most 2.6, or at most 2.7, or at most 2.8, or at most 2.9, or at most 3.0, or within a range of values obtained by combining any two of the above endpoints. The first polyether polyol may have a molecular weight of 400g/mol to 5,000g/mol, or 500g/mol to 4,000g/mol, or 600g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a numerical range obtained by combining any two of the above endpoints. For example, the first polyether polyol may be prepared by polymerizing one or more alkylene oxides selected from the group consisting of: ethylene Oxide (EO), propylene Oxide (PO), butylene oxide, tetrahydrofuran, trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylol benzene, triethylol isocyanurate, condensation products of polyhydroxy alcohols, and any combination thereof. Suitable examples of the first polyether polyol include, but are not limited to, polypropylene glycol (PPG), polyethylene glycol (PEG), polytetramethylene ether glycol (PTMEG), and any combination thereof. Alternatively, the polyether polyol may be a combination or copolymer of PEG and at least one other polyether polyol as described above. For example, the polyether polyol may be a combination of PEG with at least one of PPG, polytetramethylene glycol, and PTMEG. According to embodiments of the present disclosure, the amount of the first polyether polyol described above may be 0 to 50 wt%, or up to 40 wt%, or up to 30 wt%, or up to 20 wt%, or up to 10 wt% of the total weight of the first polyol.
According to embodiments of the present disclosure, the first polycarbonate polyol has a hydroxyl functionality of at least 1.8, at least 2.0, or at least 2.1, or at least 2.2, or at least 2.3, or at least 2.4, or at least 2.5, or at most 2.6, or at most 2.7, or at most 2.8, or at most 2.9, or at most 3.0, or within a range of values obtained by combining any two of the endpoints. The first polycarbonate polyol may have a molecular weight of 500g/mol to 5,000g/mol, or 600g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a numerical range obtained by combining any two of the above endpoints. For example, the polycarbonate polyols may include those derived from butanediol, hexanediol, and cyclohexanedimethanol. In the above embodiments, the amount of the first polycarbonate polyol may be from 10 wt% to 50 wt%, such as from 15 wt% to 45 wt%, or from 20 wt% to 40 wt%, or from 25 wt% to 35 wt%, or up to 40 wt%, or up to 30 wt%, or up to 20 wt%, or up to 10 wt%, or up to 5 wt%, or up to 2 wt%, or up to 1 wt%, or 0 wt%, or within a range of values obtained by combining any two of the above endpoints, based on the total weight of the first polyol.
According to an embodiment of the present disclosure, the content of (b) the first polyol is 30 to 70 wt%, based on the total weight of isocyanate component (a), such as in the range of values obtained by combining any two of the following endpoints: based on the total weight of isocyanate component (a), 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, and 70 wt%.
Polyol component (B)
According to various embodiments of the present disclosure, the polyol component comprises at least one second polyol selected from the group consisting of: carboxylic acid functionalized polyols having hydroxyl groups and acid side groups, phosphorus functionalized polyols comprising at least one phosphate group, second polyester polyols, second polyether polyols, and any combination thereof.
According to one embodiment of the present disclosure, the second polyol comprises a combination of a phosphorus-functionalized polyol, a second polyester polyol, and a second polyether polyol. According to another embodiment of the present disclosure, the second polyol comprises a combination of a carboxylic acid functionalized polyol, a phosphorus functionalized polyol, a second polyester polyol, and a second polyether polyol.
According to embodiments of the present disclosure, the second polyester polyol has a hydroxyl functionality of at least 1.8, at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at most 2.3, or at most 2.4, or at most 2.5, or at most 2.6, or at most 2.7, or at most 2.8, or at most 2.9, or at most 3.0, or within a range of values obtained by combining any two of the endpoints above. The second polyester polyol may have a molecular weight of 500g/mol to 5,000g/mol, or 600g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a numerical range obtained by combining any two of the above endpoints. The above description of the source, method of preparation, class, molecular structure and various parameters of the first polyester polyol also applies to the second polyester polyol. According to embodiments of the present disclosure, the content of the second polyester polyol may be 20 wt% to 60 wt%, based on the total weight of the polyol component (B), such as within a range of values obtained by combining any two of the following endpoints: 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt% and 60 wt% based on the total weight of the polyol component (B).
According to embodiments of the present disclosure, the second polyether polyol has a hydroxyl functionality of from 1.8 to 3.0, such as at least 1.8, at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at least 2.3, or at most 2.4, or at most 2.5, or at most 2.6, or at most 2.7, or at most 2.8, or at most 2.9, or at most 3.0, or within a range of values obtained by combining any two of the above endpoints. The second polyether polyol may have a molecular weight of 400g/mol to 5,000g/mol, or 500g/mol to 4,000g/mol, or 600g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a numerical range obtained by combining any two of the above endpoints. The above description of the source, method of preparation, class, molecular structure and various parameters of the first polyether polyol also applies to the second polyether polyol. According to embodiments of the present disclosure, the amount of the above-described second polyether polyol may be 30 wt% to 70 wt%, based on the total weight of polyol component (B), such as within a range of values obtained by combining any two of the following endpoints: based on the total weight of the polyol component (B), 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt% and 70 wt%, or within a range of values obtained by combining any two of the above endpoints.
According to an embodiment of the present disclosure, the phosphorus-functionalized polyol is represented by formula I:
wherein R is 1 Is trivalent C 1 -C 16 An alkylidene group or a trivalent poly (alkylene oxide) moiety having a Mn of 90 to 8,000, and R 2 、R 3 、R 4 And R is 5 Independently selected from the group consisting of: H. (C) 1 -C 12 ) Alkyl and hydroxy- (C) 1 -C 12 ) An alkylene group, provided that R 2 、R 3 、R 4 And R is 5 At least two of which are hydrogen. R is R 2 、R 3 、R 4 And R is 5 Each of which is independentIs selected from the group consisting of: h and hydroxy- (C) 1 -C 12 ) Alkylene groups such as hydroxy-methylene groups, hydroxy-ethylene groups, hydroxy-propylene groups, hydroxy-butylene groups, hydroxy-pentylene groups, hydroxy-hexylene groups, and the like. In a preferred embodiment of the present disclosure, R 2 、R 3 、R 4 And R is 5 Is hydrogen.
In the context of the present disclosure, the term "trivalent C 1 -C 16 Alkylidene group "means a group having 1 to 16 carbon atoms and three hydrogen atoms are respectively attached to" -OR "as shown in formula I 2 ”、“-OR 3” And "-O-P (=o) (OR 4 )(OR 5 ) "covalently substituted alkylidene groups. For example, trivalent C 1 An alkylidene group refers to a methylene group having the molecular structure:
trivalent C 1 An alkylidene group.
According to particular embodiments of the disclosure, R 1 May be trivalent C 1 -C 16 Alkylidene groups, or trivalent C 2 -C 15 Alkylidene groups, or trivalent C 3 -C 14 Alkylidene groups, or trivalent C 4 -C 12 Alkylidene groups, or trivalent C 5 -C 10 Alkylidene groups or trivalent C 6 -C 8 An alkylidene group.
In the context of the present disclosure, the term "trivalent poly (alkylene oxide) moiety" refers to a moiety represented by formula IV:
wherein R is 6 Is trivalent C 1 -C 16 Alkylidene groups as described above, such as trivalent C 1 -C 16 Alkylidene groups, or trivalent C 2 -C 15 Alkylidene groups, or trivalent C 3 -C 14 Alkylidene groups, or trivalent C 4 -C 12 Alkylidene groups, or trivalent C 5 -C 10 Alkylidene groups or trivalent C 6 -C 8 An alkylidene group;
R 7 、R 8 and R is 9 Each of which independently represents C 1 -C 16 Alkylene groups, such as C 2 -C 14 Alkylene groups, or C 2 -C 12 Alkylene groups, or C 2 -C 10 Alkylene groups, or C 2 -C 8 Alkylene groups, or C 2 -C 6 Alkylene or C 3 -C 4 An alkylene group; and
n 1 、n 2 and n 3 Independently represents an integer of 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
According to embodiments of the present disclosure, the trivalent poly (alkylene oxide) moiety has an Mn of 90 to 8,000, such as in the range of values obtained by combining any two of the following endpoints: 90. 100, 200, 300, 400, 500, 600, 700, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500, 4800, 5000, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, and 8000. According to a preferred embodiment of the present disclosure, the trivalent poly (alkylene oxide) moiety of formula IV above is derived from alkoxylated glycerin.
According to an embodiment, the phosphorus-functionalized polyol of formula I is included as the main ingredient of the polyol component (B).
According to an embodiment, the polyol component (B) comprises a phosphorus-functionalized polyol of formula I and does not comprise a carboxylic acid-functionalized polyol represented by formula II. According to another embodiment, the polyol component (B) comprises from 1 to 20 wt% of the phosphorus-functionalized polyol of formula I, based on the total weight of the polyol component (B). For example, the amount of phosphorus-functionalized polyol may be in the range of values obtained by combining any two of the following endpoints, based on the total weight of polyol component (B): 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%.
According to an embodiment of the present disclosure, the carboxylic acid-functionalized polyol of formula II is a compound having at least one acid side group and more than one hydroxyl end group.
For example, in formula II, R a Is a carboxylic acid group or an ester/salt thereof; r is R b Selected from the group consisting of: H. hydroxy, carboxylic acid/ester/salt groups, C 1 -C 6 Alkyl group and C 1 -C 6 An alkoxy group; and a is selected from the group consisting of: carbon, (C) 2 -C 100 ) Alkylene chains, polyalkylene oxide chains having a molecular weight of 500 to 3,000 and polyester chains having a molecular weight of 500 to 3,000. Wherein A is (C 2 -C 100 ) In embodiments of alkylene chains, polyalkylene oxide chains or polyester chains, R a And R is b Each of which may be independently connected to (C) 2 -C 100 ) An alkylene chain, a polyalkylene oxide chain or a polyester chain, and further carboxyl groups, such as one to nineteen further carboxyl groups, may be attached to (C 2 -C 100 ) -on any carbon atom of an alkylene chain, a polyalkylene oxide chain or a polyester chain.
According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II has a molecular weight of 500g/mol to 5,000g/mol, or 600g/mol to 4,000g/mol, or 700g/mol to 3,000g/mol, or 800g/mol to 2,000g/mol, or 1,000g/mol to 1,500g/mol, or within a range of values obtained by combining any two of the above endpoints. According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II has a hydroxyl functionality of from 1.8 to 2.5, such as at least 1.8, or at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at most 2.3, or at most 2.4, or at most 2.5, or within a range of values obtained by combining any two of the endpoints above. According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II has a carboxyl functionality of 1 to 20, such as at least 2, or at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10, or at most 11, or at most 12, or at most 13, or at most 14, or at most 15, or at most 16, or at most 17, or at most 18, or at most 19, or at most 20, or within a range of values obtained by combining any two of the above endpoints, wherein carboxyl functionality refers to the average number of carboxyl groups (including carboxylic acid groups, carboxylate groups, and carboxylate groups) in one molecule represented by formula II.
According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II may be a monomeric compound such as 2-carboxy-propylene glycol, 2-carboxy-2-methyl-propylene glycol, 2-carboxy-butylene glycol, 2-carboxy-2-methyl-butylene glycol, 2-carboxy-pentylene glycol, 3-carboxy-pentylene glycol, and the like.
According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II may be a polyalkylene-based compound. In such polyols of formula II, A is (C 2 -C 100 ) Alkylene chain, R a And R is b Can be connected to (C) 2 -C 100 ) -any carbon atom of the alkylene chain.
According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II may be a polyether-based compound. In such polyols of formula II, A is a polyalkylene oxide chain having a molecular weight of 500 to 3,000 and R a And R is b May be attached to any carbon atom of the polyalkylene oxide chain.
According to embodiments of the present disclosure, the carboxylic acid-functionalized polyol of formula II may be a polyester-based compound. In such polyols of formula II, A is a polyester chain having a molecular weight of 500 to 3,000 and R a And R is b May be attached to any carbon atom of the polyester chain.
By acid side group is meant a side group comprising at least one carboxyl group (which may be present in the form of a free carboxylic acid group, carboxylate salt, carboxylate ester, or a combination thereof) laterally attached to a carbon of a monomer compound, polyalkylene chain, polyalkylene oxide chain, or polyester backbone. For example, a pendant group comprising at least one carboxyl group may also be introduced by: for example, one or more hydroxyl groups attached to one or more carbons of the monomer compound, polyalkylene chain, polyalkylene oxide chain, or polyester backbone are modified with an anhydride. The acid anhydride used for the above modification is not particularly limited, and examples thereof include trimellitic anhydride, phthalic anhydride, maleic anhydride, and pyromellitic anhydride. The acid modification rate derived from the anhydride is based on the total weight of the polyol of formula II. More specifically, the proportion of the acid anhydride may be 0.3 parts by weight or more and less than 10 parts by weight, preferably 0.4 parts by weight or more and less than 5 parts by weight and more preferably 0.5 parts by weight or more and less than 5 parts by weight based on 100 parts by weight of the polyol of formula II. According to embodiments of the present disclosure, the molar content of carboxylic acid groups may be 0.1 to 30 mole%, such as 0.2 to 25 mole%, or 0.3 to 20 mole%, or 0.4 to 15 mole%, or 0.5 to 10 mole%, based on the total molar amount of carboxylic acid groups and hydroxyl groups contained in the polyol of formula II. For example, the molar content of carboxylic acid groups may be in a range of values obtained by combining any two of the following value points: based on the total molar amount of carboxylic acid groups and hydroxyl groups contained in the polyol of formula II, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, 0.6 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 5.5 mol%, 6 mol%, 7 mol%, 8 mol%, 10 mol%, 12 mol%, 15 mol%, 17 mol%, 18 mol%, 19 mol%, 20 mol%.
According to an embodiment, the carboxylic acid-functionalized polyol of formula II is used in combination with the phosphorus-functionalized polyol of formula I. According to one embodiment, the polyol component (B) comprises 0 to 30 wt% of the carboxylic acid-functionalized polyol, based on the total weight of the polyol component (B). For example, the amount of carboxylic acid-functionalized polyol may be in the range of values obtained by combining any two of the following endpoints, based on the total weight of polyol component (B): 0 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%.
According to a preferred embodiment of the present disclosure, polyol component (B) comprises only a mixture of carboxylic acid-functionalized polyol, phosphorus-functionalized polyol, second polyester polyol and second polyether polyol, and does not comprise any other polyol. According to another preferred embodiment of the present disclosure, polyol component (B) comprises only a mixture of phosphorus-functionalized polyol, second polyester polyol and second polyether polyol, and does not comprise any other polyol. According to less preferred embodiments of the present disclosure, the polyol component (B) may further comprise one or more additional and conventional polyols, such as polycarbonate polyols, polyacrylic polyols, ethylene-vinyl acetate polyols, silicone polyols, and the like.
Application of SL adhesive composition
According to various embodiments of the present disclosure, the two-part adhesive compositions of the present disclosure may comprise one or more solvents or may be completely solvent-free. As disclosed herein, the terms "solvent free", "solvent free" or "non-solvent" are used interchangeably and should be construed as a mixture of all raw materials used to prepare the adhesive composition comprising less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.2 wt%, more preferably less than 0.1 wt%, more preferably less than 100ppm parts by weight, more preferably less than 50ppm parts by weight, more preferably less than 10ppm parts by weight, more preferably less than 1ppm parts by weight of any organic or inorganic solvent based on the total weight of the mixture of raw materials. As disclosed herein, the term "solvent" refers to organic and inorganic liquids whose function is to dissolve only one or more solid, liquid or gaseous materials without initiating any chemical reaction.
According to various embodiments of the present disclosure, the weight ratio between isocyanate component (A) and polyol component (B) may be 100 (15-90). When the total amount of the isocyanate component (a) is 100 parts by weight, the amount of the polyol component (B) may be 15 parts by weight to 90 parts by weight, such as in a numerical range obtained by combining any two of the following endpoints: 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, and 90 parts by weight.
As described above, the isocyanate component (a) and the polyol component (B) are transported and stored separately, and are compounded shortly before or immediately before application during the manufacture of the laminate. In some embodiments, the isocyanate component and the polyol component are liquids at ambient temperature. When it is desired to use the adhesive composition, the isocyanate component and the polyol component are brought into contact with each other and mixed together. Once mixed, a polymerization (curing) reaction occurs between the free isocyanate groups in isocyanate component (a) and the hydroxyl groups in polyol component (B) to form a polyurethane that exhibits the function of an adhesive in the adhesive layer between the at least one first substrate and the at least one second substrate. The adhesive composition formed by contacting component (a) and component (B) may be referred to as a "curable mixture".
One or more catalysts may optionally be used to promote or accelerate the polymerization of the prepolymer described above for preparing isocyanate component (a) and/or the polymerization between the prepolymer of (a) and polyol component (B).
The catalyst may include any substance that can promote the reaction between isocyanate groups and hydroxyl groups. Without being limited by theory, the catalyst may include, for example, glycinate; a tertiary amine; tertiary phosphines such as trialkyl phosphines and dialkylbenzyl phosphines; morpholine derivatives; piperazine derivatives; chelates of various metals such as those obtainable from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like with metals such as Be, mg, zn, cd, pd, ti, zr, sn, as, bi, cr, mo, mn, fe, co and Ni; acidic metal salts of strong acids such as ferric chloride and stannic chloride; salts of organic acids with various metals, such as alkali metals, alkaline earth metals, al, sn, pb, mn, co, ni, and Cu; organotin compounds such as tin (II) salts of organic carboxylic acids, for example, tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, and tin (II) dilaurate, and dialkyltin (IV) salts of organic carboxylic acids, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate; bismuth salts of organic carboxylic acids, such as bismuth octoate; organometallic derivatives of trivalent and pentavalent As, sb and Bi, and metal carbonyls of iron and cobalt; or mixtures thereof.
Typically, the catalyst is used herein in an amount greater than zero and up to 1.0 wt%, preferably up to 0.5 wt%, more preferably up to 0.05 wt%, based on the total weight of all reactants.
The SL adhesive compositions of the present disclosure may optionally comprise any further auxiliaries and/or additives for specific purposes.
In one embodiment of the present disclosure, one or more of the adjuvants and/or additives may be selected from the group consisting of: other cocatalysts, surfactants, tougheners, flow modifiers, diluents, stabilizers, plasticizers, catalyst deactivators, dispersants, and mixtures thereof.
A method of producing a laminate using the adhesive composition is also disclosed. In some embodiments, the adhesive composition (such as the adhesive compositions discussed above) is in a liquid state. In some embodiments, the composition is liquid at 25 ℃. Even if the composition is solid at 25 ℃, the composition may be heated as needed to convert it to a liquid state. A layer of the composition is applied to the surface of a substrate or film. A "substrate/film" is any structure that is 0.5mm or less in one dimension and 1cm or more in both other dimensions. The polymer film is a film made of a polymer or a polymer mixture. The composition of the polymer film is typically 80% by weight or more of one or more polymers. In some embodiments, the thickness of the layer of curable mixture applied to the film is from 1 μm to 5 μm.
A method for preparing a laminate comprising the steps of: (a) Providing at least one first substrate and at least one second substrate; and (b) bonding the first substrate and the second substrate together by using the solvent-free adhesive composition of the present disclosure, wherein each of the first substrate and the second substrate is independently selected from the group consisting of: metal foil, polymer layer, fabric layer, and combinations thereof.
The polymer that may be used for the first substrate/second substrate may be selected from the group consisting of: PE, HDPE, LDPE, PP, PVC, PET, PU, PV, PMA, PA, ABS, CA, EPDM, EVA, CPP, and any combination or copolymer thereof.
The metal that may be used for the first substrate/second substrate may be selected from the group consisting of: al, al alloys, fe, steel, copper alloys, mg alloys, and any combination or alloy thereof.
According to one embodiment of the present disclosure, each of the first substrate and the second substrate may have a thickness of about 1 μm to 500 μm, such as within a range of values obtained by using any two of the following values: 1 μm, 2 μm, 5 μm, 6 μm, 7 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm, 20 μm, 24 μm, 25 μm, 30 μm, 32 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 72 μm, 75 μm, 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 150 μm, 180 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm and 500 μm.
According to another embodiment of the present disclosure, the SL adhesive layer may have a thickness of about 1 μm to 300 μm, such as within a range of values obtained by using any two of the following values: 1 μm, 2 μm, 5 μm, 6 μm, 7 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm, 20 μm, 24 μm, 25 μm, 30 μm, 32 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 72 μm, 75 μm, 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 150 μm, 180 μm, 200 μm, 250 μm and 300 μm.
In some embodiments, the surface of another substrate/film is contacted with a layer of curable mixture to form an uncured laminate. The adhesive composition may be applied by a conventional laminator, such as a Labo-Combi 400 machine from Nordmeccania. The curable mixture is then cured or allowed to cure. The uncured laminate may be subjected to pressure, for example by passing through a nip roller, which may or may not be heated. The uncured laminate may be heated to accelerate the curing reaction. Suitable substrates/films include woven and non-woven natural or synthetic fabrics, metal foils, polymers, metal coated polymers and polymers filled with various fillers and/or reinforcing agents. The film optionally has a surface on which an image is printed with ink; and the ink may be contacted with the adhesive composition. In some embodiments, the substrate/film is a polymer film or a metal coated polymer film, and more preferably is a combination of one metal foil and one polymer film. According to a preferred embodiment of the present disclosure, the laminate is a packaging material comprising a polymer layer, a metal film and an adhesive layer sandwiched therebetween, wherein the packaging material is preferably a food packaging material.
The process of the present disclosure may be performed continuously or batchwise. An example of a continuous process is a roll-to-roll process, in which a roll of substrate/film is unwound and transported through two or more stations in which an isocyanate component (a) and a polyol component (B) are mixed to form an adhesive composition (curable mixture) of the present application that is applied to the surface of the substrate/film. The adhesive composition (curable mixture) of the present application may be applied more than once to achieve the desired film thickness or composition distribution. The foil layer may be applied to the curable adhesive layer with or without the aid of a roller. Heating or irradiation means may be arranged to promote curing of the coated adhesive layer and rollers may also be used to enhance the bond strength within the laminate. The foil layer may also be unwound from a roll. The length of the unwound substrate/film and foil may be 10 to 20,000 meters, 10 to 15,000 meters and preferably 20 to 10,000 meters and is typically transported at a speed in the range of 0.1 to 60 meters/minute, preferably 3 to 45 meters/minute, more preferably 5 to 15 meters/minute. At the end of the continuous process, the cured laminate product is wound on a spindle.
The laminated (packaging) materials disclosed herein may be cut or otherwise shaped to have a shape suitable for any desired purpose, such as packaging materials.
Examples
Some embodiments of the invention will now be described in the following examples, in which all parts and percentages are by weight unless otherwise indicated. However, the scope of the present disclosure is of course not limited to the formulations described in these examples. Rather, the examples are merely illustrative of the present disclosure.
The information on the raw materials used in the examples is set forth in table 1 below:
TABLE 1 raw materials used in the examples
Preparation examples of isocyanate component A
The isocyanate components (urethane prepolymers) A1 to A4 of the inventive preparation example (ipex.) and the comparative preparation example (cpex.) a was synthesized according to the following procedure using the relative amounts of the starting materials listed in table 2 (in weight percent based on the total weight of the isocyanate components).
The isocyanate component (urethane prepolymer) was synthesized in a 1L glass reactor. Specifically, diisocyanate monomers as shown in table 2 were introduced into the reactor and maintained at 60 ℃ under nitrogen protection. The polyester diol shown in table 2 and additional polyol (such as polyether diol and polycarbonate polyol, if present) are then introduced into the reactor. The temperature of the reactor was slowly raised to 80 ℃ to 90 ℃ and maintained at that temperature until the theoretical NCO content was reached. The isocyanate component thus produced (i.e., the urethane prepolymer) is charged into a sealed container with nitrogen protection for further use.
TABLE 2 formulation of component A
IPEx.A1 IPEx.A2 IPEx.A3 IPEx.A4 CPEx.A
HMDI 45 55 55
IPDI 52
MF200C 100
Bester 648 29.4 35 35 32
Bester 115 20 10
Voranol CP450 4.5 3
XCPA-320 4.5
UP-100 9.6 10
Totals to 100 100 100 100
Preparation example of polyol component B
The polyol components B1 to B4 of the inventive preparation example (ipex.) and the comparative preparation example (cpex.) were synthesized by thoroughly blending the raw materials listed in table 3 (in weight percent based on the total weight of the polyol components) according to their specific amounts at ambient temperature.
TABLE 3 formulation of component B
IPEx.B1 IPEx.B2 IPEx.B3 IPEx.B4 CPEx.B
Bester 115 35 45 35
Voranol CP450 55 40 40
MF C411 90
Intermediates 88-102 95
MF88-138 10 10 5 10 5
HA-0135A 10 15
Totals to 100 100 100 100 100
Examples 1 to 5 and comparative example 1
The adhesive compositions of examples 1 to 5 and comparative example 1 were synthesized by using the isocyanate component and the polyol component prepared in the above preparation examples according to the following table 4. Laminates were prepared by using these adhesives in a Labo-Combi 400 machine from nod meik company under the following processing conditions: the line speeds were set at 120mpm and 150mpm, the transfer roll temperature was 45 ℃, the roll temperature was 60 ℃, and the coating weight was set at 1.8gsm. Different substrates were selected to form PET/Al and CPP/Al, where the PET substrate had a thickness of 12 μm, the CPP substrate had a thickness of 65 μm and the Al foil had a thickness of 7 μm.
Table 4: formulations of examples 1 to 5 and comparative example 1
Formulation of Molar (mol)Ratio of
Example 1 IPEx.A1/IPEx.B1 100:35
Example 2 IPEx.A2/IPEx.B2 100:25
Example 3 IPEx.A3/IPEx.B3 100:50
Example 4 IPEx.A4/IPEx.B4 100:50
Example 5 IPEx.A4/IPEx.B2 100:40
Comparative example 1 CPEx.A/CPEx.B 30:100
The Bond Strength (BS) and heat seal strength (HS) of these laminates were characterized by using the following techniques.
Testing technique
Bond Strength (BS)
The laminate prepared with the adhesive composition was cut into 15mm wide strips for T-peel testing at 250mm/min crosshead speed using a 5940series single column bench system (5940 Series Single Column Table Top System) available from instron corporation (Instron Corporation). During the test, the tail of each strip was gently pulled with a finger, ensuring that the tail was held 90 degrees from the peel direction. Three strips were tested for each sample and the average was calculated. The results are expressed in units of N/15 mm. Higher values indicate better bond strength.
Intensity of Heat Seal (HS)
The laminate prepared with the adhesive composition was heat sealed in an HSG-C heat sealer available from Brugger Company (Brugger Company) at a sealing temperature of 140 ℃ and a pressure of 300N for 1 second, then cooled and cut into 15mm wide strips for heat seal strength testing at 250mm/min crosshead speed using a 5940series single column bench system available from instron Company. Three strips were tested for each sample and the average was calculated. The results are expressed in units of N/15 mm. Higher values indicate better heat seal strength.
Cooking treatment
The laminate prepared with the adhesive composition was cut into 8cm x 12cm pieces, which were heat sealed to form bags having morton (Moton) soup therein, which was a blend of vinegar, tomato paste, and oil=1:1:1. The bag is then steamed for 30 minutes, then any defects of the bag, such as tunneling, delamination or leakage, are inspected, and the extent of the defects (if any) is recorded. The sample passing the test should show no signs of tunneling, delamination or leakage. The bags were opened, emptied and cooled, and then cut into 15mm wide strips to test their T-peel bond strength and heat seal strength in an Instron 5943 machine. Three strips were tested for each sample and the average was calculated.
The bond strength, heat seal strength and BiB characteristics are summarized in table 5 from which it can be seen that all inventive examples exhibited excellent HS and BS without deteriorating to an unacceptable extent even after the retort process, whereas comparative examples exhibited much higher HS and BS deterioration after the retort process.
Table 5 shows the results (in N/15 mm)
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Claims (10)

1. A solvent-free adhesive composition, the solvent-free adhesive composition comprising:
(A) An isocyanate component comprising a prepolymer, the prepolymer being the reaction product of reactants comprising: (a) At least one monomeric cycloaliphatic isocyanate compound comprising at least one cyclohexyl (cyclohexylene) group and at least two isocyanate groups; and (b) at least one first polyol selected from the group consisting of: a first polyester polyol, optionally a first polyether polyol, optionally a first polycarbonate polyol, and combinations thereof, wherein the prepolymer comprises more than one free isocyanate group; and
(B) A polyol component comprising at least one second polyol selected from the group consisting of: carboxylic acid functionalized polyols having hydroxyl groups and acid side groups, phosphorus functionalized polyols comprising at least one phosphate group, second polyester polyols, second polyether polyols, and any combination thereof.
2. The solvent-free adhesive composition of claim 1, wherein the monomeric cycloaliphatic isocyanate compound is selected from the group consisting of: isophorone diisocyanate (IPDI), methylene-bis (cyclohexyl isocyanate) (HMDI), and combinations thereof.
3. The solvent-free adhesive composition of claim 1, wherein
The phosphorus-functionalized polyol is represented by formula I
Wherein R is 1 Is trivalent C 1 -C 16 An alkylidene group or a trivalent poly (alkylene oxide) moiety having a Mn of 90 to 8,000, and R 2 、R 3 、R 4 And R is 5 Independently selected from the group consisting of: H. (C) 1 -C 12 ) Alkyl and hydroxy- (C) 1 -C 12 ) An alkylene group, provided that R 2 、R 3 、R 4 And R is 5 At least two of which are hydrogen; and is also provided with
The carboxylic acid functionalized polyol is represented by formula II
Wherein R is a Is a carboxylic acid group or an ester/salt thereof; r is R b Selected from the group consisting of: H. hydroxy, carboxylic acid/ester/salt groups, C 1 -C 6 Alkyl group and C 1 -C 6 An alkoxy group; and a is selected from the group consisting of: carbon, (C) 2 -C 100 ) Alkylene chains, polyalkylene oxide chains having a molecular weight of 500 to 3,000 and polyester chains having a molecular weight of 500 to 3,000.
4. The solvent-free adhesive composition of claim 1, wherein the content of (a) monomeric cycloaliphatic isocyanate compound is 30 to 70 weight percent and the content of (b) first polyol is 30 to 70 weight percent, based on the total weight of the isocyanate component (a); and is also provided with
The first polyol comprises 50 to 100 wt% of the first polyester polyol, based on the total weight of the first polyol.
5. The solvent-free adhesive composition of claim 1, wherein the (B) polyol component comprises 20 to 60 wt% of the second polyester polyol, 30 to 70 wt% of the second polyether polyol, 1 to 20 wt% of the phosphorus-functionalized polyol, and 0 to 30 wt% of the carboxylic acid-functionalized polyol, based on the total weight of the (B) polyol component.
6. The solvent-free adhesive composition of claim 1, wherein the isocyanate component (A) and the polyol component (B) are present in a weight ratio of 100 (15-90).
7. The solvent-free adhesive composition of claim 1, wherein
The first polyester polyol has an average functionality of 1.8 to 3 and a molecular weight of 500 to 5,000;
the first polyether polyol has an average functionality of 1.8 to 3 and a molecular weight of 400 to 5,000;
the first polycarbonate polyol has an average functionality of 1.8 to 3 and a molecular weight of 500 to 5,000;
the carboxylic acid-functionalized polyol has an average hydroxyl functionality of from 1.8 to 2.5, an average carboxylic acid functionality of from 1 to 20, and a molecular weight of from 100 to 4,000;
the second polyester polyol has an average functionality of 1.8 to 3 and a molecular weight of 500 to 5,000; and
the second polyether polyol has an average functionality of 1.8 to 3 and a molecular weight of 400 to 5,000.
8. The solvent-free adhesive composition of claim 1, wherein the (a) isocyanate component optionally further comprises (c) at least one secondary isocyanate compound other than the monomeric cycloaliphatic isocyanate compound, the secondary isocyanate compound selected from the group consisting of: c (C) 2 -C 16 Aliphatic diisocyanates, C 5 -C 18 Alicyclic diisocyanates, carbodiimide-modified isocyanates, allophanate-modified isocyanates, or combinations thereof; and/or
The solvent-free adhesive composition is free of any polymerized units derived from (meth) acrylic esters, (meth) acrylic acid, polylactones, polyolefins, bisphenol resins, silane coupling agents, and vinyl acetate.
9. A laminate comprising at least one first substrate, at least one second substrate, and at least one adhesive layer sandwiched therebetween, wherein the adhesive layer is derived from the solvent-free adhesive composition of any one of claims 1 to 8, and each of the first substrate and the second substrate is independently selected from the group consisting of: metal foil, polymer layer, fabric layer, and combinations thereof.
10. A method of producing the laminate of claim 9, the method comprising:
(a) Providing at least one first substrate and at least one second substrate; and
(b) Bonding the first and second substrates together by using the solvent-free adhesive composition according to any one of claims 1 to 8.
CN202180100199.3A 2021-07-30 2021-07-30 Solvent-free adhesive composition and laminate made therewith Pending CN117642477A (en)

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